US3395135A - Poly - Google Patents

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Publication number
US3395135A
US3395135A US322495A US32249563A US3395135A US 3395135 A US3395135 A US 3395135A US 322495 A US322495 A US 322495A US 32249563 A US32249563 A US 32249563A US 3395135 A US3395135 A US 3395135A
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US
United States
Prior art keywords
butynediol
poly
homopolymer
tetrahydrofuran
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US322495A
Inventor
Wiley E Daniels
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GAF Chemicals Corp
Original Assignee
General Aniline and Film Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US322495A priority Critical patent/US3395135A/en
Priority to US322506A priority patent/US3271378A/en
Priority to GB45013/64A priority patent/GB1021948A/en
Priority to DE19641520013 priority patent/DE1520013A1/en
Application granted granted Critical
Publication of US3395135A publication Critical patent/US3395135A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/26—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of manganese, iron group metals or platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F38/00—Homopolymers and copolymers of compounds having one or more carbon-to-carbon triple bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/116—Flare contains resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/12—High energy fuel compounds
    • Y10S149/121—Containing B, P or S

Definitions

  • This invention relates to poly(butynediol), a new polymer of 2-butynediol-1,4 having several useful commercial applications.
  • the polymer is insoluble in water, alcohols, tetrahydrofuran and benzene. It is infusible and probably crosslinked to some degree.
  • the infrared spectrum of poly (2-butynediol-1,4) showed a very strong hydroxyl absorption at 3320 cmr
  • the adsorption showed two bands located at 995 and 1020 cm.-
  • the 1020 cm. band originated from the OH deformation of the --CH OH group.
  • the polymer has the following structure:
  • EXAMPLE II 0.22 gram of poly(butynediol) was fashioned into a pellet of 12.9 mm. in diameter and 1.5 mm. in thickness in a Loomis press at 3.8 tons/sq. in. The pellet showed a specific resistance of x10 megohms-cm. at C., and 2.0 10 megohm-cm. at C. These results clearly indicate the semi-conducting properties of the poly (butynediol).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Description

3,395,135 POLY(2-BUTYNEDIOL-1,4)
Wiley E. Daniels, Easton, 1%., assignor to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Nov. 8, 1963, Ser. No. 322,495
1 Claim. (Cl. 26091.3)
This invention relates to poly(butynediol), a new polymer of 2-butynediol-1,4 having several useful commercial applications.
I have discovered that when 2-butynediol-1,4 is refluxed with a solution of bis (triphenylphosphine) nickel bromide, prepared in accordance with the procedure described by Venanzi, Jour. Chem. Soc., 719, 1958, in substantially pure tetrahydrofuran in a system open to the atmosphere for about 24 hours, a light colored solid polymer is obtained which is insoluble in water, alcohols and benzene. The polymer, poly(butynediol) or poly(2-butynediol-1,4), which are synonymous, is useful in semiconductors, rocket fuel compositions, and as a chemical intermediate.
The following examples will illustrate the preparation of poly(2-butynediol-1,4) and its application:
EXAMPLE I A solution of grams of bis (triphenylphosphine) nickel bromide and 86 grams (1.0 mole) of 2-butynediol-1,4 in 250 mls. of purified tetrahydrofuran was refluxed in a system open to the atmosphere for 24 hours. A light colored solid was precipiated at the end of this time. It was then filtered, washed with water several times and the solid dried at 70 mm. of mercury for several days. The amount of bright solid polymer was approximately 3 grams.
The polymer is insoluble in water, alcohols, tetrahydrofuran and benzene. It is infusible and probably crosslinked to some degree. Elementary analysis, after correction for catalyst end group residues, showed 55.3% of carbon, 5.5% of hydrogen, and 39.2% of oxygen by diiference, whereas the atomic formula (C H O of the poly(2-butynediol-1,4) requires (calculated) 55.7% of carbon, 6.9% of hydrogen and 37.2% of oxygen by difference.
The infrared spectrum of poly (2-butynediol-1,4) showed a very strong hydroxyl absorption at 3320 cmr The C=C-- stretching vibration was very strong at 1580 cm.- The adsorption showed two bands located at 995 and 1020 cm.- The 1020 cm. band originated from the OH deformation of the --CH OH group. The polymer has a weak adsorption at 688 cm.- which can be assigned nited States Patent 3,395,135 Patented July 30, 1968 to CH out of plane deformation vibration of cis HC=CH. The polymer has the following structure:
EXAMPLE II 0.22 gram of poly(butynediol) was fashioned into a pellet of 12.9 mm. in diameter and 1.5 mm. in thickness in a Loomis press at 3.8 tons/sq. in. The pellet showed a specific resistance of x10 megohms-cm. at C., and 2.0 10 megohm-cm. at C. These results clearly indicate the semi-conducting properties of the poly (butynediol).
EXAMPLE III One gram of poly(butynediol) and one gram of potassium nitrate were mixed and ground to a powder. The powder was packed tightly in a test tube and the tube heated until ignition of the powder took place. At this point, the powder burned fiercely with evolution of a great amount of heat, light (flame) and smoke. These results indicate the utility of poly(butynediol) as a useful component in a solid rocket fuel composition.
I claim:
1. A light colored solid homopolymer of Z-butynediol- 1,4 which is infusible and insoluble in water, alcohols, tetrahydrofuran and benzene, said homopolymer obtained by the process which consists of refluxing for 24 hours a solution of 2-butynediol-1,4 and bis(triphenylphosphine) nickel bromide in purified tetrahydrofuran and recovering the said homopolymer.
References Cited UNITED STATES PATENTS 2,542,417 2/ 1951 Kleinschmidt 260-611 JOSEPH L. SCHOEER, Primary Examiner.
H. WING, 111., Assistant Examiner.

Claims (1)

1. A LIGHT COLORED SOLID HOMOPOLYMER OF 2-BUTYNEDIOL1,4 WHICH IS INFUSIBLE AND INSOLUBLE IN WATER, ALCOHOLS, TETRAHYDROFURAN AND BENZENE, SAID HOMOPOLYMER OBTAINED BY THE PROCESS WHICH CONSISTS OF REFLUXING FOR 24 HOURS A SOLUTION OF 2-BUTYLNEDIOL-1,4 AND BIS(TRIPHENYLPHOSPHINE) NICKEL BROMIDE IN PURIFIED TETRAHYDROFURAN AND RECOVERING THE SAID HOMOPOLYMER.
US322495A 1963-11-08 1963-11-08 Poly Expired - Lifetime US3395135A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US322495A US3395135A (en) 1963-11-08 1963-11-08 Poly
US322506A US3271378A (en) 1963-11-08 1963-11-08 Process of polymerizing acetylene and derivatives thereof
GB45013/64A GB1021948A (en) 1963-11-08 1964-11-04 Improvements in or relating to the polymerization of acetylene and derivatives thereof
DE19641520013 DE1520013A1 (en) 1963-11-08 1964-11-06 Poly (2-butynediol-1,4) and process for its preparation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US322495A US3395135A (en) 1963-11-08 1963-11-08 Poly
US322506A US3271378A (en) 1963-11-08 1963-11-08 Process of polymerizing acetylene and derivatives thereof

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US3395135A true US3395135A (en) 1968-07-30

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US322506A Expired - Lifetime US3271378A (en) 1963-11-08 1963-11-08 Process of polymerizing acetylene and derivatives thereof
US322495A Expired - Lifetime US3395135A (en) 1963-11-08 1963-11-08 Poly

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Application Number Title Priority Date Filing Date
US322506A Expired - Lifetime US3271378A (en) 1963-11-08 1963-11-08 Process of polymerizing acetylene and derivatives thereof

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US (2) US3271378A (en)
DE (1) DE1520013A1 (en)
GB (1) GB1021948A (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3405110A (en) * 1964-03-02 1968-10-08 Gaf Corp Poly(propynol) prepared using a nickel dicarbonyl di(triphenylphosphine) in an inert non-hydroxylated organic solvent
US4228060A (en) * 1978-11-03 1980-10-14 Allied Chemical Corporation Polymerization of acetylene
DE3046802A1 (en) * 1980-12-12 1982-07-15 Basf Ag, 6700 Ludwigshafen ETHYLENE-ALKINE COPOLYMERISATES, THEIR PRODUCTION AND USE AS AN ADDITION TO PETROLEUM DISTILLATES
US4496700A (en) * 1983-08-08 1985-01-29 Union Carbide Corporation Polymerization of haloalkynes by a nickel catalyst
US4687823A (en) * 1986-07-01 1987-08-18 The Dow Chemical Company Alkynyl-bridged poly(arylcyclobutene) resins
KR910002946A (en) * 1989-07-28 1991-02-26 오노 알버어스 Propargyl aromatic ether polymer and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2542417A (en) * 1949-12-10 1951-02-20 Gen Aniline & Film Corp Hexamethyl benzene compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2542417A (en) * 1949-12-10 1951-02-20 Gen Aniline & Film Corp Hexamethyl benzene compounds

Also Published As

Publication number Publication date
GB1021948A (en) 1966-03-09
DE1520013A1 (en) 1969-12-04
US3271378A (en) 1966-09-06

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